Certain carbamoyloxyimino-azolidines

ABSTRACT

Compounds of the formula   WHEREIN Q is sulphur, sulphoxide, sulphone, or oxygen, and X or Y is   USEFUL AS PESTICIDES.

United States Patent 1 Punja 1 Oct. 22, 1974 1 CERTAINCARBAMOYLOXYIMINO-AZOLIDINES [75] Inventor: Nazim Punia, Wokingham,England [73] Assignee: Imperial Chemical Industries Limited, London,England i221 Filed: May4, 1972 [211 Appl. No; 250,119

[30] Foreign Application Priority Data May 7 1971 Great Britain 13723/71[521 US. Cl. 260/3067, 71/67, 260/2948 E,

[56] References Cited UNITED STATES PATENTS 3681,47) 8/1972 Gutmun260/3067 Primary Examiner-R. Gallagher 1 Attorney, Agent. orFirm-Cushmzm, Darby & Cushman [57] ABSTRACT Compounds of the formulawherein Q is sulphur, sulphoxide, sulphone, or oxygen, and X or Y isuseful as pesticides.

5 Claims. No Drawings ILY Wherein Q is oxygen or sulphur, or thesulphoxide or sulphone group; R, R and R", which may be the same ordifferent, are hydrogen, or unsubstituted, or substituted, hydrocarbylor heterocyclic radicals; and either (i) X is a group of formula:

where R and R which may be the same or different, are hydrogen, orunsubstituted, or substituted, hydrocarbyl radicals, or the acylresidues of carboxylic'orsulphur-containing acids; and Y is oxygen,sulphuror the hydrocarbylimino radicalgor (ii) Y is a group of forwhereR and R which may be the same or different, are hydrogen, orunsubstituted, or substituted, hydrocarbyl radicals, or the acylresidues of carboxylic or sulpur-containing acids; and X is oxygen,sulphur, or the hydrocarbylimino radical.

In one aspect the invention also provides compounds of formula:

wherein R, R and R are hydrogen atoms or unsubstituted, or substituted,hydrocarbyl groups; n has the value zero, one or two; and wherein either(i) X is a group of formula:

6 where R and R are hydrogen or hydrocarbyl groups,

and Y is oxygen or sulphur or the hydrocarbylimino group; or (ii) Y is agroup of the formula:

where R and R" are hydrogen or hydrocarbyl groups, and X is oxygen orsulphur or the hydrocarbylimino group.

Preferred compounds are those provided by the invention of formula:

wherein Q is oxygen, or sulphur, or the sulphoxide or sulphone group; Rand R which may be the same or diffrent are hydrogen or alkyl; R ishydrogen, alkyl, alkenyl, alkylthioalkyl, alkyl-substituted amino,aralkyl, ester-substituted alkyl, or a halo-substitutednitrogencontaining aromatic monocyclic heterocycle; and either (i) X isa group of formula:

where R and R which may be the same or different,

are hydrogemalkyl, phenyl, halo-substituted phenyl, acyl, haloalkyl,alkoxyalkyl or alkylthioalkyl; and Y is oxygen, sulphur or alkylimino;or (ii) Y is a group of formula: v

where R and R, which may be the same or different, are hydrogen, alkyl,phenyl, halo-substituted phenyl, acyl, haloalkyl, alkoxyalkyl oralkylthioalkyl; and X is oxygen, sulphur or alkylimino.

In a more preferred aspect the invention provides compounds of formula:V

Wherein Q is an oxygen or sulphur atom, or the sulphoxide or sulphonegroup; R and R, which may be the same or different are hydrogen oralkyl; R is hydrogen, alkyl, alkenyl, alkylthioalkyl, alkyl-substitutedamino, aralkyl, ester-substituted alkyl, or a halo-substitutednitrogen-containing aromatic monocyclic heterocycle; and R and R whichmay be the same or different, are hydrogen, alkyl, phenyl,halo-substituted phenyl, acyl, haloalkyl, alkoxyalkyl or alkylthioalkyl.

In an even more preferred aspect the invention provides compounds offormula:

wherein R and R which may be the same or different are hydrogen oralkyl; R is hydrogen, alkyl, alkenyl. alkylthioalkyl, alkyl-substitutedamino, aralkyl, estersubstituted alkyl, or a halo-substitutednitrogencontaining aromatic monocyclic heterocycle; and R and R whichmay be the same or different, are hydrogen, alkyl, phenyl,halo-substituted phenyl, acyl, haloalkyl, alkoxyalkyl or alkylthioalkyl.

In a even yet more preferred aspect the invention provides compounds offormula:

wherein R and R', which may be the same or different, are hydrogen, oralkyl containing up to four carbon atoms; R is hydrogen, alkylcontaining up to eight carbon atoms, allyl, benzyl, dimethylamino,methylthiomethyl, ethoxycarbonylmethyl, or halo-substituted pyridyl; andR and R which may be the same or different, are hydrogen, methyl,phenyl, chlorosubstituted phenyl, acetyl, chloromethyl, methoxymethyl,ethoxymethyl or ethylthiomethyL Especially preferred compounds are thosehaving the formula:

are set out in Table 1 below, where the meanings of R,

R R, R and R are given together with a melting point (m.p.) eachcompound expressed in degrees centigrade.

TABLE I M.1., Compound No. R R R R R C.

H H CI'I2CH CH3)2 CH 1-1 122 1'1 H CH3 CH3 11 216 H H C3115 CH3 H 218CH3 CH3 CH3 CH3 H 134.5 11 1'1 71-C3H17 CH3 11 126 H H n-C H CH C11 52CH3 CH3 CH3 CH CH 137 CH C11 11 C113 .11 240 CH3 H C113 CH3 I1 138 CHCH3 C2115 C113 H 107 H H CH3 CH3 CH 168 CH3 CH3 CH(CH3)2 CH3 11 [)7 CH3CH3 CH'ZSCITZ CH 10G CH CH3 H CH3 COCH: 161 CH CH3 CHgCH CHg CH3 H 76CHzCH(CH3)2 H CH3 CH3 H 130 C3H5 11 CH3 C113 11 CH3 CH3 CH3 C 11 11. J8CH(CH3)2 H CH3 CH3 H 120 C311 C3115 H CH3 H 162 CH2CH(CH )2 H C2115 CH3H 100 C3115 C311 CH3 CH3 I1 104 H CH3 N(CH3)2 CH3 I1 118 CH(CH3)2 11 3H5CH H 91 C2H5 n-CJI I1 CH3 H 145 Cal-I5 n-CJIq CH3 CH3 .11 Oil CH3 CH3 CHH 11 H H CH3 C H 140 CH CH3 CH2CsH5 CH3 11 CH3 CH3 CH CH(CH3)2 CH3 H 103C113 CH3 CH COOCgHa CH3 e11 112 CH3 C 11 CH3 CH3 .11 8O CH CH3 CH3 CH3CHgCl 1 12 CH3 CH C113 C113 ClIgSCgHg 74 CH3 C113 C11 CH ()lIgOClh llii36 CH3 CH3 CH3 CH3 ClIgOCgll (i8 37 CH CH3 CH3 H 143 38 CH2CH(CH3)3 H HCH3 H 39- CH(CH3)2 11 H CH3 H 120 40 C2115 H H CH3 H 105 41 CH3 CH3 Cl FCH3 H 210 Cl F 42 CH3 CH3 C1I3COC(CH3)3 CH3 H 164 *Snblimes at 300.

. s ln another aspect the invention PfOl/ldes compounds 1 H of formula:ll N NCO-N= :l x k y N-oo-1\ J i wherein R, R and R are alkyl groupscontaining up ((5)11 k: to four carbon atoms; and R and R are hydrogenor V alkyl groups containing up to four carbon atoms. A furwherein 1 2and a are alkyl groups Containing up ther specific compound of thepresent invention is that to four carbon atoms; R and R are hydrogen oralkyl having the formula: containing up to four carbon atoms, and n hasthe value one or two. 0 is f Specific compounds according to theformula:

' o CH3 B2 on R 0 l a The invention com ounds ma be re ared b treatc 0 NP Y P P Y 8 F mg an oxlme of formula:

R2 3 1 I are set out in Table 2 below, whef the meanings of R, A= 1 R RR and R are given, together with the value of Q, n and a melting pointfor each compound.

TABLE 2 Compound No. R R2 R-1 R R n mp. C

43 CH, CH, CH, CH, H 2 us 7 43A CH CH CH, CH, H 1 & 2 Oil in anotheraspect the invention provides compounds WhereinR, R R and Q have any ofthe meanings as of formula: I defined hereinbefore and either (i) A isgroup N-OH and B is oxygen, sulphur or a hydrocarbylimino group,

R3 ,or (ii) 8 is group N-OH and A is oxygen sulphur or ahydrocarbylimino group, with a carbamoylating agent. R4 0 i Y 5 N H Suchagents include isocyanates, carbamoylhalides, N -0 S and phosgene withammonia or an amine. R5 Thus the invention provides a process for theprepac. R2 ration of compounds of the formula:

wherein R, R and R are alkyl groups containing up R3 0 to four carbonatoms; R and R are hydrogen or alkyl R4 0 L l groups comprising up tofour carbon atoms; and Y is a sulphur atom or an alkylimino groupcontaining up to 1 t four carbon atoms. R2 Specific compounds accordingto the formula:

R3 Y wherein R, R R and R have any ofthe meanings as 4 0 L definedhereinbefore and wherein R is hydrogen which comprises treating an oximeof formula:

R1 S s 5 R2 R3 O r 1 I i are set out in Table 3 below, where themeanings of Y, HON= R, R, R, R and R are given together with a melting sR1. point for each compound. 11

TABLE3 Compound No. R R2 R R R Y m.p. C

44 CH3 CH CH, H CH, s. in 45 CH, CH CH CH, CH, s 21x 46 CH, CH, CH CH HNC,H, Oil

In another aspect the invention provides compounds with an isocyan'ateof formula:

of formula: R -N=C=O The invention also provides a process for thepreparation of a compound of the formula:

wherein R, R R, R and R have any of the meanings as defined hereinbeforeexcept that R and R cannot be hydrogen, which comprises treating anoxime of formula:

or bromine atom. I

The invention also provides a process for the preparation of a compoundof formula:

wherein R, R R, R and R have any of the meanings as definedhereinbefore, which comprises treating an oxime of formula:

with phosgene and then bringing the product of such treatment intoreaction with an amine of formula RR NH.

Such carbamoylation reactions are as outlined above are convenientlycarried out in the presence of a base. Suitable bases include tertiaryamines, for example triethylamine, or diethylaniline, aprotic nitrogenheterocycles for example pyridine or N-methylmorpholine, and alkalimetal carbonates for example potassium carbonate. The reactions may alsobe carried out in the presence of a solvent, or diluent, preferably anonhydroxylic solvent, for example, chloroform, pyridine, aromatichydrocarbons or petroleum ether.

Compoundsof formula:

may also be prepared by the treatment of a compound of formula:

with a halogen compound of formula R Hal, conveniently in the presenceof a base, for example sodium hydride. Compounds of formula:

wherein R, R R R and R have any of the meanings as defined hereinbeforeand n has the value one or two may be prepared by the oxidation of acompound of formula:

with an oxidising agent, for example, hydrogen peroxide in the presenceof an acid, for example acetic acid. Compounds of formula:

may be prepared by any of the carbamoylation procedures outlined abovefrom an oxime of formula:

I o N N{ Invention compounds of formula:

wherein R is an acyl group may be obtained by treating an inventioncompound of formula:

with an acylating agent, for example an acyl halide.

Invention compounds of formula:

' 9 10 wherein R is a chloromethyl group may be obtained by The thionesof formula: treatment of a compound of formula: R3

I p o f 7 R5NI-IPJ0-N= j S C t ,7 m maybe obtained by the well-knownmethod oi reacting with formaldehyde and hydrogen chloride. together aCompound of formula:

Such chloromethylated compounds may be subse- 10 S quently reacted withalcohols and thiols to yield inven- RQNLFyLSH tion compounds wherein Ris alkoxyalkyl or alkylthioalkyl. (usually in the form of a metal orammonium salt The oximes used as intermediates in the preparation h f) ih a h l id f f l of the invention compounds may be obtained by treatl5ment of the corresponding thiones with hydroxylif amines, thus forexample a compound of formula: lifll- I H 0 L where Hal [5 a halogenatom. An alternative method of preparing the oximes of s 1 formula: I .7o 4 N or HON= s l R1 R3 R2 i a j particularly those wherein R" 18 ahydrogen atom, in- 0 F volves the treatment of an imine of formula:

W t i I f 0 N wherein R, R and R have any of the meanings as de- .finedhereinbefore, may be treated with hydroxylamine S R1 to yield an oximeof formula: 1'1

Ba 0 with hydroxylamine. Such imines may be obtained by l 1 the reactionof a thiourea of formula:

HON= l s S 40 NHg()NI-IR i W 2 or With a haloacid of formula:

| R N l 11 :I IIal-C-OOOH 0 FR! ft I The thiones of formula:

Similarly a compound of formula: Ra

R3 1 vl g i S: I R1 B2 v R R2 7 l Where Y IS sulphur may be obtainedfrom the thrones where Y, R, R and R have any of the meanings as deofformula: fined hereinbefore, may be treated with hydroxylamine R3 togive the oxime of formula: I 0

. N Ra S= Y L O 5 HON by treating the latter with phosphoruspentasulphide. If desired the thioncs of formula:

| o N 1 s m may first be treated with an amine to yield a compound offormula:

Where Y is hydrocarbylimino, before the treatment with phosphoruspentasulphide.

The compounds of this invention or compositions as hereinafter definedmay be used to combat a variety of insect and other invertebrate pestsincluding the following:

'I'L'Imnychus Ielarius Aphis fabne Aedes aegypli Megoura viciac Pierirbrassime IIulellu maz'ulipennis Pllaedun corhlcariae (red spider mite)(black aphid) (mosquito) (green aphid) (white butterfly larva) (diamondback moth larva) (mustard beetle) Calandra granuria (grain beetle)Trihalium clmfusum (flour beetle) Musca domestica (housefly) Bluirellagermanim (cockroach) Agriulimax reliculamr (grey field slug) Meloidogyneinmgnila (nematodes) A particularly useful feature of the activity ofthe invention compounds is their ability to act as systemic pesticides,that is to say, their ability to move through a plant to combatinfestations thereon at a site remote from the site of application ofthe compound.

,The compounds and compositions of this invention may also be used tocontrol a variety of plant pathogens including the following fungaldiseases of plants:

(rust on wheat) (late blight on tomato) (downy mildew on vine) (powderymildew on apple) (powdery mildew on vine) (blast on rice) (grey mould onvine) Pucciniu remmlila Pliymplitlmra infestunx Plasmoparu vin'cvlaPodurphaeru lcumIric/m Uncinula neralor Piriculariu uryzm' Bvrrylircinerea Some of the compounds have algicidal properties. Compounds ofthe invention may also be used as herbicides, and are preferably used athigher rates of application for this purpose.

The compounds of the invention may be used to combat pests on their ownbut are more conveniently used in the form of a composition whichcomprises in addition to an invention compound, a diluent or carriermaterial.

In a further aspect therefore the invention provides a pesticidalcomposition comprising as an active ingredient a compound of formula:

wherein Q is oxygen or sulphur, or the sulphoxide or sulphone group; R,R and R, which may be the same or different, are hydrogen, orunsubstituted. or substituted, hydrocarbyl or heterocyclic radicals; andeither (i) X is a group of formula:

where R" and R which may be the same or different, are hydrogen, orunsubstituted or substituted, hydrocarbyl radicals, or the acyl residuesof carboxylic or sulphurcontaining acids; and Y is oxygen, sulphur, orthe hydrocarbylimino radical; or (ii) Y is a group of formula:

where R and R which may be the same or different, are hydrogen, orunsubstituted or substituted, hydrocarbyl radicals, or the acyl residuesof carboxylic or sulphur-containing acids; and X is oxygen, sulphur, orthe hydrocarbylimino radical.

in a preferred aspect the invention provides a pesticidal compositioncomprising as an active ingredient a compound of formula:

wherein R and R which may be the same or different are hydrogen oralkyl; R is hydrogen, alkyl, alkenyl, alkylthioalkyl, alkyl-substitutedamino, aralkyl, estersubstituted alkyl, or a halo-substitutednitrogencontaining aromatic monocyclic heterocycle; and R and R'', whichmay be the same or different, are hydro- 13 gen, alkyl, phcnyl,halo-substitutcd phcnyl, acyl, haloalkyl, alkoxyalkyl or alkylthioalkyl.

In an even more preferred aspect the invention provides a pesticidalcomposition comprising as an active ingredient a compound of formula:

Wherein R is alkyl containing up to four carbon atoms; R and'R arehydrogen or alkyl containing up to four carbon atoms; R is hydrogen ormethyl; and R is methyl.

In an especially preferred aspect the invention provides a pesticidalcomposition comprising as an active ingredient the compound having theformula:

The compositions may be used for agricultural or horticultural purposesand the type of composition used in any instance will depend upon theparticular purpose for which it is to be used.

The compositions may be in the form of dusting powders wherein theactive ingredient is mixed with a solid diluent or carrier. Suitablesolid diluents or carriers may be, for example, kaolin, bentonite,kieselguhr, dolomite, calcium carbonate, talc, powdered magnesium,Fullers earth, gypsum, Hewitts earth, diatomaceious earth and chinaclay.

The compositions may also be in the form of liquid preparations to beused as dips or sprays which are generally aqueous dispersion ofemulsions containing the active ingredient in the presence of one ormore wetting agents, dispersing agents, emulsifying agents or suspendingagents.

Wetting agents, dispersing agents and emulsifying agents may be of thecationic, anion or non-ionic type. Suitable agents of the cationic typeinclude, for example quaternary ammonium compounds, for example,cetyltrimethylammonium bromide. Suitable agents of the anionic typeinclude, for example, soaps, salts of aliphatic mono-esters of sulphuricacid, for example sodium lauryl sulphate, salts of sulphonated aromaticcompounds, for example sodium dodecylbenzenesulphonate, sodium, calcium,or ammonium lignosulphonate, butylnaphthalene sulphonate, and a mixtureof the sodium salts of diisopropyland triisopropylnaphthalene sulphonicacids. Suitable agents of the non-ionic type include, for example, thecondensation products of ethylene oxide with fatty alcohols such asoleyl alcohol or cetyl alcohol or with alkyl phenols such asoctylphenol, nonylphenol and octylcresol. Other non-ionic agents are thepartial esters derived from long chain fatty acids and hexitolanhydrides, the condensation products of the said partial esters withethylene oxide, and the lecithins. Suitable suspending agents are, forexample, hydrophilic colloids, for example polyvinylpyrrolidone andsodium carboxymethylcellulose,

and the vegetable gums, for example gum acacia and gum tragacanth.

The aqueous dispersions or emulsions may be prepared by dissolving theactive ingredient or ingredients in an organic solvent which may containone or more wetting, dispersing or emulsifying agents and then addingthe mixture so obtained to water which may likewise contain one or morewetting, dispersing or emulsifying agents. Suitable organic solvents areisopropyl alcohol, propylene glycol, diacetone alcohol, toluene,kerosene, methylnaphthalene, xylenes and trichloroethylene.

The compositions to be used as sprays may also be in the form ofaerosols wherein the formulation is held in a container under pressurein the presence of a propellant such as fluorotrichloromethane ordichlorodifluoromethane.

By the inclusion of suitable additives for example for improving thedistribution, adhesive power and resistance to rain on treated surfaces,the different compositions can be better adapted for the various usesfor which they are intended.

The compositions which are to be used in the form of aqueous dispersionsor emulsions are generally supplied in the form of a concentratecontaining a high proportion of the active ingredient or ingredients,the said concentrates to be diluted with water before use. Theseconcentrates are often required to withstand storage for prolongedperiods and after such storage, to be capable of dilution with water inorder to form aqueous preparations which remain homogeneous for asufficient time to enable them to be applied by conven tional sprayequipment. The concentrates may contain 10-85 percent by weight of theactive ingredient or ingredients.

When diluted to form aqueous preparations, such preparations may containvarying amounts of the active ingredient or ingredients depending uponthe purpose for which they are to be used.

For agricultural or horticultural purposes, an aque' ous preparationcontaining between 0.0001 percent and 0.1 percent by weight of theactive ingredient or ingredients may be used.

The compositions of the present invention may, if desired, also comprisein addition to a compound of the present invention, at least one otherbiologically active ingredient, for example, in insecticide, or afungicide.

Thus, for example, a composition of the present invention may comprise acompound of the present invention together with the gamma isomer ofl,2,3,4,5,6- hexachlorocyclohexane.

In use, the invention compounds of compositions 5 may be used to combatpests in a variety of ways. Thus the pests themselves, or the locus ofthe pests or the pest habitat may be treated to control the pests.

In a further feature therefore the invention provides a method ofcombating pests wherein the pests, the locus of the pests, or thehabitat of the pest is treated with a compound or a compositionaccording to the invention.

The invention also provides a method of treating plants with a compoundof composition according to the invention to render them lesssusceptible to damage by pests, which may already be occurring (i.e.treatment to eradicate an infestation or infection) or which is expectedto occur (i.e. treatment to protect the plant from an infestation orinfection).

In a yet further feature, therefore, the invention provides a method oftreating plants to render them less susceptible to damage by pests,which comprises treating the plants, or the seeds, corms, bulbs, tubers,rhizomes or other propagative parts of the plants, with a compound orcomposition according to the invention.

EXAMPLE 1 This example illustrates the preparation of 3,5,5- trimethylthiazolidin-4-one-2-thione having the formula:

To a solution of methylamine in ethanol (33% w/v, 20 ml.) was added (40ml.) and the mixture was cooled to C, whilst carbon disulphide (7.6 g)in ethanol ml.) was added with stirring over a period of 5 minutes.After stirring for a further minutes ethyl 2-bromoisobutyrate (19.4 g)was added over 5 minutes after which the mixture was refluxed for 3hours. The mixture was then cooled and kept at the ambient temperaturefor 18 hours. After removal of the ethanol by evaporation undcr reducedpressure the residual solid was treated with water (100 ml), collectedby filtration, washed with water and recrystallised from aqueous ethanolto give 3,5,5-trimethylthiazolidin-4-one-2-thione, melting at 96C.

EXAMPLE 2 Compounds of formula:

| O N I S R R' R R Physical Characteristic H H CH.,CH(CH m.p. 115C H HCH, m.p. 7 l-72C H H C H, viscous Oil -Continued R R R PhysicalCharacteristic H CH CH b.p. 100C/0.4 mm. 2 n z s H m.p. 16C. CH C H,, CHm.p. 62C CH CH N(CH m.p. 74C H H n-C,.H, viscous Oil.

EXAMPLE 3 This example illustrates the preparation of 5,5-dimethyl-2-imino-thiozolidin-4-one, having the formula:

s ea:

A mixture of thiourea (19.0 g) and ethanol (150 ml) was refluxed untilall the thiourea had dissolved. Ethyl 2-bromo-iso-butyrate (49.0 g.) wasthen added over 10 minutes to the refluxing solution, after which themixture was refluxed for 6 hours, kept at the ambient temperature for 18hours and the ethanol removed by evaporation at reduced pressure. Theresidue was treated with water and then with aqueous sodium bicarbonatesolution to adjust the pH to 7. The precipitated solid was collected byfiltration, washed with water and dried to yield5,5-dimethyI-Z-imino-thiazolidin-4-one,

' melting at 258C.

EXAMPLE 4 melting at EXAMPLE 5 This example illustrates the preparationof 2- oximino-3,5,5-trimethylthiazolidin-4-one, having the formula:

3,5,5-Trimethylthiazolidin-4-one-2-thione (62.0 g), hydroxylaminehydrochloride (75.0 g), pyridine (75.0 ml) and ethanol (750 ml) wererefluxed together for 8 hours. The mixture was cooled and diluted withwater. The precipitate was collected by filtration and recrystallisedfrom a mixture of benzene and petroleum ether to yield2-oximino-3,5,5-trimethyl-thiazolidin-4-one having a melting point of216C.

EXAMPLE 6 By a p sqqu simi to at l usaats in the P ceding examplecompounds of formula:

wherein the values of R, R and R are those set out in the followingtable, were also prepared. The table also includes a melting point indegrees centigrade for each compound.

This example illustrates the preparation of 2-oximino-S,5-dimethyl-thiazolidin-4-one having the structure:

[ o N l 1I0N= S-fi CH3 EXAMPLE 8 By the use of a procedure similar tothat illustrated in the preceeding example the following compounds werealso prepared. They all conform to the formula:

and the values for R, R and R, together with a melting point in degreescentigrade are set out in the table below.

1 R m.p. C

(H CH; H 204 H CH CH(CH.1M H 160 H H I43 H CHtCH h H 159 an, cm, H 135 HCH (H I70 EXAMPLE 9 This example illustrates the preparation of 3,5,5trimethyl-2-methyl-carbamoyloxyiminothiazolidin- 4-one, (Compound No. 4,Table I) having the formula:

l5 2-Oximino-3,5,5-trimethylthiazolidin-4-one (15.0 g) was suspended inchloroform and methyl isocyanate (5.0 g) added, together withtriethylamine (4 drops). After keeping for 4 hours at room temperaturethe solvent was evaporated at reduced pressure and the residual solidrecrystallised from benzene to yield 3,5,5-trimethyl-2-methylcarbamoyloxyiminothiazolidin- 4-one, having a meltingpoint of l34.5C.

EXAMPLE 10 A similar procedure to that illustrated in the preceedingexample was used for the preparation of the following compounds, usingthe appropriate intermediate oxime as follows:

3-isopropyl-2-methylcarbamoyloxyiminothiazolidin- 4-one (Compound No. 1,Table 1) from 3- isopropyl-2-oximinothiazolidin-4one;3-methyl-2-methylcarbamoyloxyiminothiazolidin- 4-one (Compound No. 2,Table I) from 3-methyl- 2-oximinothiazolidin-4-one;3-ethyl-2-methylcarbamoyloxyiminothiazolidin- 4 -one (Compound No. 3,Table I) from 3-ethyl-2- oximinothiazolidin-4-one;3-n-octyl-2-methylcarbamoyloxyiminothiazolidin- 4-one (Compound No. 5,Table i) from 3-n-octyl- 2-oximinothiazolidin-4-one;3,S-dimethyl-2-methylcarbamoyloxyiminothiazolidin4-one (Compound No. 9,Table I) from 3,5- dimethyl-2-oximinothiazolidin-4-one;3-dimethylamino-5,S-dimethyl-Z- methylcarbamoyloxyiminothiazolidin-4-one(Compound No. 23, Table l) from 3-dimethylamino-5,5-dimethyl-2-oximinothiazolidin-4-one; and3,5-dimethyl-3-ethyl-2-methylcarbamoyloxyiminothiazolidin-4-one(Compound No. 32, Table I) from3,5-dimethyl-3-ethyl-2-oximinothiazolidin- 4-one.

EXAMPLE 1 1 This example illustrates the preparation of 5,5-dimethyl-2-methylcarbamoyloxyiminothiazolidin- 4-one (Compound No. 8,Table I) having the formula:

2-Oximino-5,5-dimethylthiazolidin-4-one (4.0 g), chloroform ml), methylisocyanate (2.0 ml) and triethylamine (3 drops) were mixed and kept atroom temperature for 4 hours, after which the solvent was removed underreduced pressure. The residual solid was5,5-dimethyl-2-methylcarbamoyloxyiminothiazolidin-4-one, melting at240C.

EXAMPLE 12 A similar procedure to that illustrated in the preceedingexample was used to prepare the following compounds, using theappropriate oxime as follows:

5,5-diethyl-2-methylcarbamoyloxyiminothiazolidin- 4-one; (Compound No20, Table I) from 5,5- diethyl-2-oximinothiazolidin-4-one;5-n-butyl-5-ethyl-2-methylcarbamoyloxyiminothiazolidin-4-one (CompoundNo. 25, Table I) from 5-n-butyl-5-ethyl-2-oximinothiazolidin-4-one;

5-iso-buty-l-Z-methylcarbamoyloxyiminothiazolidin- 4-one (Compound No.38, Table I) from 5-isobutyl-2-oximinothiazolidin-4-one;

5-iso-propyl-2-methylcarbamoyloxyiminothiazolidin- 4-one (Compound No.39, Table I) from 5- isopropyl-Z-oximinothiazolidin-4-one; and

5-ethyl-2-methylcarbamoyloxyiminothiazolidin- 4-one (Compound No. 40,Table I) from 5-ethyl-2- oximinothiazolidin-4-one.

EXAMPLE 13 This example illustrates the preparation of 3-n-octyl-2-dimethylcarbamoyloxyiminothiazolidin-4-one (Compound No. 6, Table I),having the formula:

2-oximino-3-n-octylthiazolidin-4-one (4.5 g) was suspended in drybenzene (150 ml) and sodium hydride (1.0 g of 50 percent dispersion inmineral oil) added in small portions at room temperature. After theinitial efferves'cence had ceased the mixture was refluxed for 30minutes and then cooled. Dimethylcarbamoyl chloride (2.2 g) was thenadded and the mixture again refluxed for 60 minutes, after which themixture was cooled, poured into water, the benzene layer separated,washed with water, and dried over anhydrous magnesium sulphate. Afterfiltration the filtrate was evapaorated under reduced pressure and theresidual solid recrystallised from petroleum ether to yield 3-n-octyl-2-dimethylcarbamoyloxyiminothiazolidin-4-0ne having a melting point of52C.

EXAMPLE 14 By a procedure similar to that illustrated in the preceedingexample the following compounds were also prepared from the appropriateoximes:

3,5,5-trimethyl-Z-dimethylcarbamoyloxyiminothiazolidin-4-one (CompoundNo. 7, Table I) from 3,3,5-trimethyl-2-oximinothiazo1idin-4-one; and3-methyl-2-dimethylcarbamoyloxyiminothiazolidin- 4-one (Compound No. l1, Table 1) from 3-methyl- 2-oximinothiazolidin-4-one.

EXAMPLE 15 This example illustrates the preparation of 3,55trimethyl-2-methylcarbamoyloxyiminothiazolidin- 5 4-one (Compound No. 4,Table 1) having the formula:

Sodium hydride (0.05 g) was added to 5,5-dimethyl- 152-methy1carbamoyloxyiminothiazolidin-4-one (Compound No. 8, Table l;0.49 g) in dimethylformamide (25 ml). Hydrogen was evolved over a periodof about minutes after which the mixture was gently warmed for minutes.Methyl iodide (2 c.c.) was added and the mixture gently warmed for afurther minutes, after which it was cooled, poured into water andextracted with chloroform. The chloroform extract was washed with waterand dried over anhydrous magnesium sulphate. After filtration thefiltrate was evaporated at reduced pressure and the resultant oiltriturated with n-hexane to yield 3,5,5-trimethyl-2-methylcarbamoyloxyiminothiazolidin-4-one, identical with the productobtained by the method of Example EXAMPLE 16 By a procedure similar tothat illustrated in the proceeding example there were prepared otherinvention compounds from the appropriate reactants as follows:

3-ethyl-5,5-dimethy1-2-methylcarbamoyloxyiminothiazolidin-4-one(Compound No. 10, Table l) from5,5-dimethyl-2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 8,Table 1) and ethyl iodide;

3-iso-propyl-5,5-dimethyl-2-methylcarbamoyloxyiminothiazolidin-4-one(Compound No. 12, Table 1) from5,5-dimethyl-2-methylcarbamoyloxyiminothiazo1idin-4-one (Compound No. 8,Table I) and iso-propylbromide;

3'methylthiomethyl-5,5-dimethyl-2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 13, Table 1) from5,5-dimethyl-2- methylcarbamoyloxyiminothiazo1idin-4-one (Compound No.8, Table I and'methyl chloromethyl thioether;

3-allyl-5,5-dimethyl-2-methylcarbamoyloxyiminothiazolidin-4-one(Compound No. 15, Table 1) from5,5-dimethyl-2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 8,Table I) and allyl bromide;

3-methyl-5-iso-propyl-2-methylcarbamoyloxyiminothiazolidin-4-one(Compound No. l6, Tab1e I) from5-iso-propyl-2-methylcarbamoyloxyiminothiazolidin-4-one, (Compound No.38, Table I) and methyl iodide;

3-methyl-5-ethyl-2-methylcarbamoyloxyiminothiazolidin-4-one (CompoundNo. 17, Table 1) from 5-ethyl2-methylcarbamoyloxyiminothiazolidin-4-one(Compound No. 40, Table l) and methyl iodide;

21 3-methyl-5-iso-propyl-2-methylcarbamoyloxyiminothiazolidin-4-one(Compound No. 19, Table 1) from-iso-propyl-2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 39,Table l) and methyl iodide;3-ethyl-5-iso-butyl-2-methylcarbamoyloxyiminothiazolidin-4-one (CompoundNo. 21, Table 1) from5-iso-butyl-2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 38,Table l) and ethyl iodide;3-methyl-5,5-diethyl-2-methylcarbamoyloxyiminothiazolidin-4-one(Compound No. 22, Table I) from5,5-diethyl-2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 20,Table I) and methyl iodide;3-ethyl-5-iso-propyl-2-methylcarbamoyloxyiminothiazo1idin-4-one(Compound No. 24, Table I) from5-iso-propyl-2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No.39, Table l) and ethyl iodide:3-methyl-5-n-butyl5-ethyl-2-methylcarbamoyloxyiminothiazolidin-4-one(Compound No. 26, Table 1) from5-n-butyl-5-ethyl-2-methylcarbamoyloxyiminothiazolidin-4-one (CompoundNo. 25, Table l) and methyl iodide; 3-benzyl-5,5-dimethyl-2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 29.Table 1) from 5,5-dimethyl-2-methylcarbamoyloxyiminothiazolidin-4-one(Compound No. 8, Table l) and benzyl chloride;3-iso-butyl-5,5-dimethyl-2-methylcarbamoyloxyiminothiazolidin-4-one(Compound No. 30, Table 1) from5,5-dimethyl-2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 8,Table I) andv iso-butyl bromide; 3-ethoxycarbonylmethyl-5,5-dimethyl-2-methylcarbamoyloxyiminothiazolidin 4-one (Compound No. 31, Table 1) from5,5-dimethyl-2- methylcarbamoyloxyiminothiazolidin-4-one (Compound No.8, Table l) and ethyl chloroacetate;

3 2,5-dichloro-2,6-difluoropyrid-4-yl )-5,5-dimethyl-2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 41, Table 1)from 5,5-dimethyl-2- methylcarbamoyloxyiminothiazolidin-4-one (CompoundNo. 8, Table I) and 3,5-dichloro-2,4,6- trifluoropyridine; and

3-pivaloylmethyl-5,S-dimethyI-Z methylcarbamoyloxyiminothiazolidin-4-one(Compound No. 42, Table 1) from 5,5-dimethyl-2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 8, Table l) andchloromethyl t-butyl ketone.

EXAMPLE 17 This example illustrates the preparation 3,5,5- trimethyl-2(N-chloromethyl-N-methylcarbamoyl)oxyiminothiazolidin-4-one (Compound No.33, Table I) having 'the formula:

To a solution of3,5,5-trimethyl-2-methylcarbamoyloxyiminothiazolidin-4-one (15.6 g) inmethylene dichlo- EXAMPLE 18 This example illustrates the preparation of3,5,5- trimethyl-2(N-ethylthiomethyLN- methylcarbamoyl)oxyiminothiazolidin-4-one pound No. 34, Table 1) having the formula:

(Com- UB3 0 CQH5SCH2 o I CH2 CH3 Ethane thiol (0.62 g) was added to asolution of sodium (0.23 g) in ethanol (25.0 ml) and to the stirredmixture was added a solution of 3,5,5-trimethyl-2(N-chloromethyl-N-methylcarbamoyl)oxyiminothiazolidin-4-one (2.7 g.) inethanol (25.0 ml) at the ambient temperature. After keeping at theambient temperature for 18 hours the volatile components were removed byevaporation under reduced pressure. The residue was treated with waterml.) and extracted with chloroform (2 X 25 ml.). The extracts werecombined, dried over anhydrous magnesium sulphate, and evaporated toyield a solid which was recrystallised from petroleum ether (boilingrange 60-80C) to yield 3,5,5-trimethyl-2(N-ethylthiomethyl-N-methylcarbamoyl)oxyiminothiazolidin-4-one, having a melting point of74C.

EXAMPLE 19 This example illustrates the preparation of 3,5,5-trimethyl-2(N-methoxymethyl-N- methylcarbamoyl)oxyiminothiazolidin-4-onepound No. 35, Table 1), having the formula:

(Com- I 3,3,5-trimethyl-2(N-chloromethyl-N- EXAMPLE 20 By a proceduresimilar to that illustrated in the previous example'the preparation ofanother invention compound was effected using the appropriate reactantsas follows:

3,5,5-trimethyl-2(N-ethoxymethyl-N-methylcarbamoyl)oxyiminothiazolidin-4-one (Compound No. 36, Table 1)from 3,5,5-trimethyl-2(N-chloromethyl-N-methylcarbamoyl)oxyiminothiazolidin-4-one (CompoundNo. 22, Table I) and ethyl alcohol.

EXAMPLE 21 This example illustrates the preparation of 3,3,5-trimethyI-Z-phenylcarbamoyloxyiminothiazolidin- 4-one (Compound No. 18,Table 1,) having the foroximinothiazolidin-4-one (2.6 g) in chloroform(50 ml) was added phenylisocyanate (1.8 g) and triethylamine (2 drops).The mixture was kept at the ambient temperature for 18'hours, afterwhich the volatile components were removed by evaporation under reducedpressure and the residual solid recrystallised from diethyl ether toyield 3,5,5-trimethyl-2- phcnylcarbamoyloxyiminothiazolidin-4-one,melting point at 98C.

EXAMPLE 22 By a similar procedure to that illustrated in the preceedingexample the following compounds were also prepared using the appropriatereactants as follows: 3-methyl-2-phenylcarbamoyloxyiminothiazolidin-4-one (Compound No. 28, Table 1) from 3-methyl-2-oximinothiazolidin-4-one and phenyl isocyanate; and

3,5,5-trimethyl-2(3,4-dichlorophenyl)carbamoyloxyiminothiazolidin-4-one(Compound No. 37, Table 1) from3,5,S-trimethyl-2-oximinothiazolidin-4-one and 3,4-dichlorophenylisocyanate.

EXAMPLE 23 This example illustrates the preparation of3,5,5-trimethyl-2-carbamoyloxyiminothiazo1idin-4-one (Compound No. 27,Table 1) having the formula:

To a solution of 3,5,5-trimethyl-2-oximinothiazolidin- 4-one (5.0 g) inchloroform (200 ml.) was added a solution of phosgene (3.0 g) in toluene(30 ml). After stirring for one hour at the ambient temperature, themixture was cooled to C and gaseous ammonia passed in for minutes. Thesolvents were removed by evaporation under reduced pressure and theresidual solid recrystallised from a mixture of toluene and petroleumether (boiling range 6()-80C) to yield a solid which did not melt, butsublimed at a temperature above 300C.

EXAMPLE 24 This example illustrates the preparation of 5,5-dimethyl-2-(N-acetyl-N-methylcarbamoyl)oxyiminothiazolidin-4-one(Compound No. 14, Table 1), having the formula:

ll 7 0 cast p E r 1 CH3 S CH:

To a solution of 5,5-dimethyl-2-methy1carbamoyloxyiminothiazolidin-4-one(1.0 g) in pyridine (20.0 ml) acetyl chloride (2.0 ml.) was added slowlywith external cooling to keep the reaction temperature below 5C. Whenthe addition had been completed the mixture was heated at C for 15minutes and then poured into iced water. The mixture was extracted withchloroform, the extracts washed with 5% w/v aqueous hydrochloric acidsolution and with water, dried over anhydrous magnesium sulphate, andevaporated under reduced pressure to yield -5,5-dimethy1-2(N-acetyl-N-methylcarbamoyl)oxyiminothiazolidin-4-one, melting at 161C.

EXAMPLE 25 This example illustrates the preparation of 3,5,5-trimethylthiazolidin-2,4-dithione having the formula:

CH3 S A mixture of 3,5,5-trimethylthiazolidin-2-one-4-thione (8.7 g),phosphorus pentasulphide (6.0 g) and dioxan ml) was refluxed withstirring for 4 hours, after which the mixture was kept at the ambienttemperature for 18 hours. The liquid was decanted, the solid residuewashed with hot dioxan (2 X 25 ml) and the washings combined with thedecanted liquid and heated with animal charcoal (5.0 g) and zinc dust(6.0 g) for 10 minutes. The mixture was filtered whilst hot, and thesolvent evaporated under reduced pressure to yield a residual solid,which was recrystallised from ethanol to yield3,5,5-trimethylthiazolidin-2,4-dithione, melting at 90C.

EXAMPLE 26 This example illustrates the preparation of 3,5,5-trimethyl-4-oximino-thiazolidin-Z-thione having the formula:

[ S N u IIO N CH3 S A mixture of 3,5,5-trimethylthiazolidin-2,4-dithione(6.0 g.), hydroxylamine hydrochloride (11.0 g.), pyridine (12.0 ml) andethanol (150 ml.) was refluxed for eight hours. Ethanol was evaporatedunder reduced pressure and water (200 ml.) added to the residue. The

mixture was extracted with chloroform (3 X 50 ml.), the combinedchloroform extracts being washed with a w/v solution of hydrochloricacid (3 X 100 ml.) and with water (100 ml.), dried over anhydrousmagnesium sulphate, and evaporated under reduced pressure to yield aresidual solid. This was recrystallised from petroleum ether (boilingrange 80l00C) to yield 3,5,5- trimethyl-4-oximinothiazolidin-2-thione,having a melting point of 142C.

EXAMPLE 27 This example illustrates the preparation of 3,5,5-trimethyl-2-n-butyl-iminothiazolidin-4-on4 having the formula:

CH: CH:

A mixture of 3,5,5-trimethy1thiazolidin-4-one-2-thione (57.8 g)n-butylamine (25.0 g) and ethanol (200 ml.)

was refluxed for eight hours, after which time the ethanol and excessmbutylamine were removed by evaporation under reduced pressure. Theresidual oil was distilled to yield3,5,5-trimethyl-2-nbutyliminothiazolidin-4-one, boiling at 90C/0.l6 mm.Hg, having n 1.5079.

EXAMPLE 28 This example illustrates the preparation of 3,5,5-trimethyl-2-n-butyliminothiazolidin-4-thione having the formula:

NC I-Iflll) N s T i om cm A mixture of3,5,5-trimethyl-2-nbutyliminothiazolidin-4-one (42.8 g) phosphoruspentasulphide (17.8 g) and dioxan (200 ml.) was refluxed for eight hourswith brisk stirring after which the liquid was decanted, heated withanimal charcoal (2.0 g.) for 10 minutes, filtered whilst hot, and thenevaporated under reduced pressure. The residual oil was distilled toyield 3,5,5-trimethyl-2-n-butyliminothiazolidin-4- thione, having aboiling point of 10l-l02C/0.22 mm.Hg.

EXAMPLE 29 This example illustrates the preparation of 3,5,5-

trimethyl-2-n-buty1imino-4-oximinothiazolidine having the formula:

N 04mm A mixture of 3,5,5-trimethyl-2-n-butyliminothiazolidin-4-thione(18.6 g) hydroxylamine hydrochloride (17.5 g) pyridine 18.2 ml.) andethanol (150 ml) was refluxed until evolution of hydrogen sulphide hadEXAMPLE 30 This example illustrates the preparation of 3,5,5-trimethyl-4-methyl-carbamoyloxyiminothiazolidin-2- thione (Compound No.44, Table 3) having the formula:

To a-solution of 3,5,5-trimethyl-4-oximinothiazolidin-2-thione (5.7 g)in chloroform ml.) was added methyl isocyanate (2.1 g) and triethylamine(3 drops). The mixture was kept at the ambient temperature for 6 hours,after which the volatile components were removed by evaporation atreduced pressure, and the residual solid recrystallised from toluene toyield 3,5,5- trimethyl-4-methylcarbamoyloxy-iminothiazolidin-2- thione,melting at 147C.

EXAMPLE 31 This example illustrates the preparation of 3,5,5-trimethyl-2-n-butylimino-4-methylcarbamoylox yiminothiazolidine(Compound No. 46. Table 3) having the formula:

gl lTNcrll'o (n) To a solution of 3,5,5-trimethyl-2-n-butylimino-4-oximinothiazolidine (2.6 g) in chloroform (50 ml.) was added methylisocyanate (3.0 ml.) at the ambient temperature, and the mixture waskept at this temperature for 18 hours. Evaporation of the volatileportion under reduced pressure yielded a viscous oil which wasidentifled by infra-red and n.m.r. spectroscopy as 3,5,5-trimethyl-2-n-butylimino-4-methylcarbamoyloxyiminothiazolidine.

EXAMPLE 32 This example illustrates the preparation of 3,3,5-trimethyl-4-dimethylcarbamoyloxyiminothiazolidin-Z- thione (Compound No.45, Table 1) having the forr'nula:

EXAMPLE 33 This example illustrates the preparation of the compound3,5,S-trimethyl-2-methylcarbamoyloxyiminothiazolidin-4-one l,l-dioxide(Compound No. 43,

Table I) having the formula:

carbamoyloxyiminothiazolidin-4-one l,l-dioxide having a melting point of118C. The petroleum ether washings were evaporated to yield an oilymixture of 3,5,5-trimethyl-2-methylcarbamoyloxyiminothiazolidin-4-onel-oxide with some of the dioxide.

EXAMPLE 34 This example illustrates the preparation of 2-oximino-3,5,5-trimethyloxazolidin-4-one having the formula:

--CI-Ia A mixture of 3,5,5-trimethyloxazolidin-4-one-2-thione (15.0'g)hydroxylamine hydrochloride (25.0 g) pyridine (27.0 g) and ethanol (200ml.) was refluxed for four hours, after which the volatile portion wasremoved by evaporation under reduced pressure. The residual oil waspoured into water (200 ml.) and the solid which precipitated out wascollected by filtration, washed with water and dried to yield2-oximino-3,5,5- trimethyl-oxazolidin-4-one, having a melting point of246C.

EXAMPLE 35 This example illustrates the preparation of 3,5,5-trimethyl-2-methylcarbarnoyloxyiminooxazolidin- 4-o ne (Compound No. 47)having the formula:

A mixture of 2-oximino-3,5,S-trimethyloxazolidin- 4-one (5.9 g)chloroform ml) and methyl isocyanate (2.2 g) was kept in a moisture freeatmosphere at the ambient temperature for 18 hours. Evaporation of thevolatile portion of the mixture under reduced pressure yielded3,5,5-trimethyl-2-methylcarbamoyloxyimino-oxazolidin-4-one, melting atC.

EXAMPLE 36 The activity of a number of the compounds was tested againsta variety of insect and other invertebrate pests. The compounds wereused in the form of a liquid preparation containing 0.1 percent byweight of the compound except in the tests with Aedes aegypri where thepreparations contained 0.01 percent by weight of the compound. Thepreparations were made by dissolving each of the compounds in a mixtureof solvents consisting of 4 parts by volume of acetone and l part by"volume of diacetone alcohol. The solutions were then diluted with watercontaining 0.01 percent by weight of a wetting agent sold under thetrade name LISSAPOL NX until the liquid preparations con tained therequired concentration of the compound. Lissapol is a Trade Mark.

The test procedure adopted with regard to each pests was basically thesame and comprised supporting a number of the pests on a medium whichwas usually a host plant or a foodstuff on which the pests feed, andtreating either or both the pests and the medium with the preparations.

The mortality of the pests was then assessed at periods usually varyingfrom one to three days after the treatment.

The results of the tests are given below in Table 4. In this table thefirst column indicates the name of the pest species. Each of thesubsequent columns indicates the host plant or medium on which it wassupported, the number of days which were allowed to elapse after thetreatment before assessing the mortality of the pests, and the resultsobtained for each of the compounds, numbered as in Tables 1 to 3 above.The assessment is expressed in integers which range from 0-3.

0 represents less than 30 percent kill 1 represents 30-49 percent kill 2represents 50-90 percent kill 3 represents over 90 percent kill A dashin Table 4 indicates that no test was carried out. The symbol Aindicates that an antifeeding effect was observed.

TABLE4 Sup- No.

Pest Species Rim of COMPOUND NO.

i days! 2 4 6 a 9 I0 11 I2 11 I5 17 w 20 22 2.1 24

Telranyz'huslelarius French 3 0 0 3 3 0 2 3 3 3 3 0 0 2 3 3 (red spidermites. Bean adults) telranyt'lmslelarius French 3 0 0 0 l 0 0 0 3 0 0 20 O 3 0 2 (red spider mites Bean (nematodes) TABLE 4 Continued Sup- No.Pest Species port of COMPOUND NO Medays dium l 2 4 6 8 9 10 ll l2 l3 l5l7 l) 20 22 23 24 Aphis fabae Broad 2 0 3 0 O 0 3 3 3 3 3 3 3 0 3 3 3(green aphids) Bean Megoura viceae Broad 2 O 3 O 0 0 3 3 3 3 0 3 3 0 3 33 (black aphids) Bean Aede: aegypli Water 1 3 O 0 3 O 2 l (l O (l 0 0 30 (I (mosquito larvae) Aerie: aegypli Ply l l (l O 2 O O l O O 0 (J (l l2 l) (mosquito adults) wood Musm domeslica Milk/ 2 2 2 (l I 0 3 0 0 2 (l2 2 l houseflies-contact Sugar test") Musca domeslica Ply 2 0 0 0 l) l Ol) (l 0 0 l) (houseflies-residual wood test") Blane/Ia germam'm l t) 0 00 2 (l l 0 3 0 3 .3

TABLE 4 Continued Sup- No Pest Species port of COMPOUND Not Me daysrLlium 26 29 30 3,1 32 3 35 36 43 43A 44 46 47 Tetranychus lelariiu'French 3 0 0 0 0 3 3 0 0 0 (l I 0 2 (red spider mites. adults) BeanTelranychu: lelurius French 3 0 0 0 0 2 0 0 0 0 0 U 0 0 (red spidermites eggs) Bean Aphis fabae Broad 2 0 O 0 0 3 3 3 0 O 0 3 O 3 (greenaphids) Bean Megoura viceae Broad 2 0 0 O 0 3 3 3 0 0 0 3 0 3 (blackaphids) Bean Aedes aegypli Water 1 O 0 0 0 3 3 0 i 0 O 0 3 3 (mosquitolarvae) Aedex aegypli Plywood l 0 2 0 2 0 0 0 O 0 0 0 2 (mosquitosadults) Musca domz'xlit'a Milk/ 2 2 0 l 0 2 0 0 0 2 l O 3(housefliescontact test") Sugar Muscu domextit'a Plywood 2 0 0 0 0 l) O0 O O (houseflies-residual test) Blane/la germanica l O O 0 O 3 3 2 O 00 0 0 3 (cochroaches) TABLE 4 -Continued Sup- No. Pest Species port ofCOMPOUND NO.

Medays di l 2 4 5 7 9 l0 ll l2 l5 l7 l8 I9 20 Zl Z2 Z3 Pieris brassicaeCab- 2 3 0 3 3 3 2 O 3 2 (l 3 3 0 (cabbage white bage A A A A A A A A AA A A caterpillars systemic test Pieris brassime Cab- 2 0 0 3 0 0 0 3 30 O 3 0 0 O 3 3 (cabbage white bage A A A A A A A caterpillars (Contacttest) Plulella maculi- Mus- 2 0 O 2 0 O 0 2 O O 0 O (l 0 O 0 penni'rtard A A A A A A A A (diamond back moth, larvae systemic test) Plulellamaculi- Mus- 2 0 O 0 D 0 0 O O 0 O 0 O 0 pennis tard A A A A diamondback moth larvae -contact test) Phaedon wchleariae Mus- 2 0 2 3 O 0 3 33 2 2 3 O 2 0 3 2 (mustard beetles tard residual test) Phaedoncochleuriae Mus- 2 3 0 0 0 (l (mustard beetles tard A A A systemic test)Calandra granuria Grain 2 0 0 O O 0 2 O 0 0 0 0 l 0 2 0 (grain beetles)'I'n'balium confusum Grain 2 0 0 0 0 0 (l (l l) (l 2 0 (flour beetles)Melvidagyne Water I 0 O 0 2 O 3 0 l) 0 0 0 .3 3 3 (l (l inmguim TABLE 4Continued Sup- No. Pest Species port of COMPOUND NO.

3 3,}, days 24 2s 29 .10 31 32 33 35 41 43 44 45 4s 47 Pierir brassicut'Cabbage 2 0 0 3 (l 0 0 2 3 O 0 (l 3 (cabbage white cater- A A A pillarssystemic test) Pieri: brarsime Cabbage 2 3 3 0 0 2 2 0 0 0 3 0 (cabbagewhite caterpillars contact test A A A A A Plulella maculipennir Mustard2 0 O 0 0 0 0 0 O 0 0 3 0 (diamond back moth. A A A larvae systemictest) Flute/Ia maculipennix Mustard 2 0 0 0 0 O (l 0 0 0 0 0 2 0(diamond back moth. A A larvae, contact test) Phaedon t'ocltleariaeMustard 2 l 0 0' O 3 O 0 0 0 l 3 (mustard beetles residual test) A A A AA A A A A Phaedrm cothleariae Mustard 2 0 0 O 3 0 0 0 0 3 3 (mustardbeetles systemic test) A A A A A Calandra granuria Grain 2 0 0 0 0 2 O OO 0 0 O 0 1 (grain beetles) Tribolium confusum Grain 2 0 0 0 0 0 2 0 0 0O 0 0 2 (flour beetles) Meloidogyne incognito Water I 0 0 0 3 0 3 O 0 03 2 g 3 2 (nematodes) In the contact test the flies are sprayeddirectly; in the residual test the flies are placed on a medium that hadpreviously been treated. In the systemic tests the preparations areapplied to the soil in which the host plants are growing EXAMPLE 37Compounds of the invention were tested for molluscicidal activity anddetails of the test conducted are as follows.

A weighed sample of the compound under test was dissolved in 0.5 cc ofan ethanol and acetone mixture (50:50 v/v). The solution was dilutedwith 0.5 cc. water and poured on to a calf feeding pellet in a glasspetri dish and the pellet was air dried for 24 hours. The weight ofcompound used was chosen so that the dried pellet contained 4 percent byweight of the active ingredient. Two replicates each consisting of aplastic petri dish containing a pellet, 2 slugs, and a moistened filterpaper to maintain a high relative humidity were used in each test. Thedishes were left in the cold room (C). After 6 days the kill wasassessed.

The slugs used were Agriolimax reticulatus (Mull), and they had beenstarved for 24 hours before the commencement of the tests. The resultsof the test are set out in Table 5 below.

The compounds of this invention were tested against a variety of foliarfungal diseases of plants. The technique employed is to spray thefoliage of the undiseased plants with a solution of the test compoundand also to drench the soil in which the plants are growing with anothersolution of the same test compound. All solutions for spraying anddrenching contained 0.01 percent of the test compound. The plants werethen infected with the diseases it was desired to control and after aperiod of days, depending upon the particular disease, the extent of thedisease was visually assessed. The results are given in Table 6A below,wherein the extent of the disease is given in the form of a grading asfollows:

Percentage Amount of Disease Grading 0 6i to l 26 to 60 2 6 to 25 3 0 to5 TABLE 6 Disease and Plant Time interval Disease Code Days Letter(Table 6A) Pucciniu IttlIlIl/illl 7 A (Wheat) Pliymp/tI/mra infcxlans 3B (tomato) Plasmopara vilicola 7 C (vine) Uncinulu m'camr l() D (vine)Piricularia oryzae 7 E (rice) Puzlusplxut'ru Ieucotrit'hu [0 F (apple)Bulrylix cinema 3 G (vine) TABLE 6A Compound No: Disease Code Letter A BD F G 2 2 l O 3 O 3 0 4 2 3 l 0 0 0 0 6 0 0 0 3 0 9 3 l 2 3 0 l 0 l5 0 l3 3 0 0 0 l6 0 l 3 0 0 0 0 l7 3 3 3 3 0 0 0 l8 0 0 0 0 (l 0 2 20 0 3 0 3l 2 0 2l 0 2 3 0 0 0 0 22 l 3 (l 0 0 l 0 24 0 3 0 3 l 2 0 TAB LE 6A 4Continued Compound No.: Disease Code Letter This example illustrates adusting powder which may be applied directly to plants or other surfacesand com prises 1 percent by weight of compound No. 4 of Table I and 99percent by weight of talc.

EXAMPLE 4O 25 Parts by weight of Compound No. 4 of Table I, 65 parts byweight of xylene, and 10 parts of an alkyl aryl polyether alcohol(Triton X-lOO; Triton is a Trade Mark) were mixed in a suitable mixer.There was thus obtained an emulsion concentrate which can be mixed withwater to produce an emulsion suitable for use in agriculturalapplications.

EXAMPLE 41 5- Parts by weight of Compound No. 4 of Table l werethoroughly mixed in a suitable mixer with 95 Parts by weight of talc.There was thus obtained a dusting powder.

EXAMPLE 42 Parts by weight of compound No. 4 of Table l, 10 parts of anethylene oxide-octylphenol condensate (Lissapol" NX; LissapoP is a TradeMark) and 80 parts by weight of diacetone alcohol were thoroughly mixed.There was thus obtained a concentrate which, in mixing with water, gavean aqueous dispersion suitable for application as a spray in the controlof insect pests.

EXAMPLE 43 This example illustrates a concentrated liquid formulation inthe form of an emulsion. The ingredients listed below were mixedtogether in the stated proportions and the whole stirred until theconstituents were dispersed.

EXAMPLE 44 The ingredients listed below were ground together in theproportions stated to produce a powdered mixture readily dispersible inliquids.

Compound No. 10 of Table l 50 Dispersol T (Dispersol" is a Trade Mark) 5China Clay 45 EXAMPLE 45 A composition in the form of grains readilydispersible in a liquid (for example water) was prepared by grindingtogether the first four of the ingredients listed below in the presenceof water and then the sodium acetate was mixed in.

The admixture was dried and passed through a British Standard meshsieve, size 44-100 to obtain the desired size of grains.

wt. Compound No. ll of Table l 50 Dispersol T [2.5 Calciumlignosulphonate 5 Sodium dodecylhenzenesulphonate 12.5 Sodium acetate 20EXAMPLE 46 A composition suitable for use as a seed dressing wasprepared by mixing all three of the ingredients set out below in theproportions stated.

wt. Compound No. l2 of Table Mineral Oil 2 China Clay 18 EXAMPLE 47 Agranular composition was prepared by dissolving the active ingredient ina solvent, spraying the solution obtained on to the granules of pumiceand allowing the solvent to evaporate.

wt. Compound No. 22 of Table or S g Pumice Granules same EXAMPLE 48 Anaqueous dispersion formulation was prepared by mixing and grinding theingredients recited below in the proportions stated.

wt. Compound No. 47 of Table l 40 Calcium lignosulphonate l0 Water 50The following constitutes an explanation of the compositions orsubstances represented by the various Trade Marks and Trade Namesreferred to in the foregoing Examples.

LUBROLL is a condensate of l mole of nonyl phenol with l3 molarproportions of ethylene oxide.

AROMASOLH is a solvent mixture of alkylbenzenes DISPERSOL' T is amixture of sodium sulphate and a condensate of formaldehyde with thesodium salt of naphthalene sulphonic acid.

LlSSAPOL' NX is a condensate of l mole: of nonyl phenol with 8 moles ofethylene oxide.

TRITON X-l00 is an alkyl aryl polyether alcohol.

I claim: 1. A compound of the formula:

substituted pyridyl; and either (i) X is a group of the formula:

where R and R which may the same or different, are hydrogen, alkylcontaining up to four carbon atoms, phenyl, chlorosubstituted phenyl,acetyl, chloromethyl, methoxymethyl, ethoxymethyl or ethylthiomethyl;and Y is oxygen, sulphur or alkylimino containing up to four carbonatoms; or (ii) Y is a group of the formula:

where R" and R", which may be the same or different, are hydrogen, alkylcontaining up to four carbon atoms, phenyl, chlorosubstituted phenyl,acetyl, chloromethyl, methoxymethyl, ethoxymethyl or ethylthiomethyl;and X is oxygen, sulphur or alkylimino containing up to four carbonatoms.

2. A compound according to claim 1 of the formula:

R3 R4\ 0 l, N t O N= j 115 S FRI R1 wherein R and R which may be thesame or different are hydrogen or alkyl containing up to four carbonatoms; R is hydrogen, alkyl containing up to eight carbon atoms, allyl,benzyl, dimethylamino, mcthylthiomethyl, ethoxy-carbonylmethyl, orhalo-substituted pyridyl; and R and R, which may be the same ordifferent, are hydrogen, chlorosubstituted phenyl, acetyl, chloromethyl,methoxymethyl, ethoxymethyl or ethylthiomethyl.

3. A compound according to claim 1 of the formula:

wherein R and R, which may be the same or different, are hydrogen, oralkyl containing up to four carbon atoms; R is hydrogen, alkylcontaining up to eight carbon atoms, allyl, benzyl, dimethylamino,methylthiomethyl, ethoxycarbonylmethyl, or halo-substituted pyridyl; andR and R which may be the same or different, are hydrogen, methyl,phenyl, chlorosubstituted phenyl, acetyl, chloromethyl, methoxymethyl,ethoxymethyl or ethylthiomethyl.

4. A compound according to claim 1 of the formula:

wherein R is alkyl containing up to four carbon atoms; R and R arehydrogen or alkyl containing up to four carbon atoms; R is hydrogen ormethyl; and R is methyl.

5. The compound according to claim 1 having the formula:

1. A COMPOUND OF THE FORMULA
 2. A compound according to claim 1 of theformula:
 3. A compound according to claim 1 of the formula:
 4. Acompound according to claim 1 of the formula:
 5. The compound accordingto claim 1 having the formula: